CN106003460B - A kind of method that directly extrusion prepares in-situ micro-fibril blend - Google Patents

A kind of method that directly extrusion prepares in-situ micro-fibril blend Download PDF

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CN106003460B
CN106003460B CN201610317924.3A CN201610317924A CN106003460B CN 106003460 B CN106003460 B CN 106003460B CN 201610317924 A CN201610317924 A CN 201610317924A CN 106003460 B CN106003460 B CN 106003460B
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fibril
screw extruder
blend
fusing point
situ micro
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CN106003460A (en
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信春玲
黄英
何亚东
姜李龙
康凯
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B29C48/402—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders the screws having intermeshing parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B29C48/425—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders using three or more screws
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

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  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a kind of method that directly extrusion prepares in-situ micro-fibril blend, including：The in-situ micro-fibril blending raw material being made up of the relatively low thermoplastic matrix resin of fusing point or flow temperature, fusing point or the higher thermoplasticity fiber-forming resin of flow temperature and processing aid is placed in vacuum drying chamber and is separately dried；Raw material is blended according to mass fraction in the dried in-situ micro-fibril; matrix phase content 95 55%; into fine phase content 5 45%; the ratio of processing aid 0 5% is separately added into multi-screw extruder of the screw rod radical more than 2; or it is proportionally added into high-speed mixer and is added after preliminary premixing in multi-screw extruder of the screw rod radical more than 2; melt temperature is less than into melting extrusion under the fusing point of fine gathering compound or flow temperature process conditions in multi-screw extruder; cooling treatment in tank is immersed afterwards; it is granulated through pelleter, prepares in-situ micro-fibril blend.The method of the present invention has equipment simple, and production technology is easily controlled, and production efficiency is high, and can efficiently prepare the in-situ micro-fibril blend with obvious strain hardening phenomenon.

Description

A kind of method that directly extrusion prepares in-situ micro-fibril blend
Technical field
The present invention relates to a kind of method that directly extrusion prepares in-situ micro-fibril blend, belong to polymeric material field.Specifically It is related to a kind of method that original position stretching-shearing alternating flow field using multi-screw extruder prepares in-situ micro-fibril blend.
Background technology
The in-situ micro-fibril blend to grow up in recent years receives much concern, particularly thermoplastic polymer (TP)/thermoplasticity Polymer (TP) in-situ microfiber-reinforced blend, during melting extrusion, dispersed phase is in the presence of shear stress, with graininess It is distributed in matrix, head extrusion thing passes through follow-up hot-stretch again, and dispersed phase deforms under the effect of extraneous tensile stress and taken To formation fibre-like morphology and through cooling and shaping, so as to obtain high performance in-situ microfiber-reinforced blend, this original is prepared at present Position fento composite mainly has two methods：" melting extrusion-solid phase stretching-annealing " method and " melting extrusion-hot-drawn Stretch-quench " method, the former production efficiency is extremely low, is only suitable for melting after extruder as theoretical study method, the latter's blend mostly Melt the steps such as extrusion, plurality of roller hot-stretch, quenching, pelletizing, there is process continuity, easily operated, production efficiency with respect to the former Height, the preparation method mainly used in patent and document prepared by the relevant in-situ micro-fibril blend found is the latter, in State's application for a patent for invention CN102532831 A (denominations of invention：It is a kind of to prepare ABS/PET alloy materials using in-situ fibrillation method Method) the ABS/PET alloys prepared using this method are disclosed, stretching and impact strength are effectively improved.
Although " melting extrusion-hot-stretch-quenching " method is to prepare the main method of in-situ micro-fibril blend now, it is given birth to Production process needs first break draft device, and equipment cost and production cost are higher, and technology controlling and process is complicated, and is limited by draw ratio, in situ Fento diameter is thicker, and draw ratio is small, and the performance raising of blend is limited.
The content of the invention
The present invention is overcome the deficiencies in the prior art, discloses a kind of method that directly extrusion prepares in-situ micro-fibril blend, Simple with equipment, production technology is easily controlled, and production efficiency is high, and can efficiently prepare with obvious strain hardening phenomenon The features such as in-situ micro-fibril blend.
The invention provides a kind of method that directly extrusion prepares in-situ micro-fibril blend, this method comprises the following steps：
Step 1：By by the relatively low thermoplastic matrix resin of fusing point or flow temperature, fusing point or the higher thermoplastic of flow temperature Property fiber-forming resin and the in-situ micro-fibril blending raw material of processing aid composition be placed in vacuum drying chamber and be separately dried；
Step 2：By dried in-situ micro-fibril blending raw material according to mass fraction, matrix phase content 95-55%, Into fine phase content 5-45%, processing aid 0-5% ratio is separately added into multi-screw extruder of the screw rod radical more than 2, or It is proportionally added into high-speed mixer and is added after preliminary premixing in multi-screw extruder of the screw rod radical more than 2, in more spiral shell Melt temperature is less than into melting extrusion under the fusing point of fine gathering compound or flow temperature process conditions in bar extruder, immerses afterwards Cooling treatment in tank, is granulated through pelleter, prepares in-situ micro-fibril blend.
The screw rod radical that heretofore described multi-screw extruder refers in an extruder barrel while install is more than 2 Extruder.Three-screw extruder as installed three screw rods in a machine barrel simultaneously, or four screw rods of four screw rods are installed simultaneously Extruder etc..In polymer blending processing, increase with screw rod radical in extruder, the high shear region of engagement of material experience or drawing Stretching area can be multiplied, using multi-screw extruder carry out blending and modifying can significantly improve shearing that polymer melt undergone or Stretching course, improve the dispersion mixing and distributed rendering effect of blend.
Especially, multi-screw extruder of the present invention refers to the del three-screw extruder engaged entirely, draw ratio More than 15.Del engages three-screw extruder compared with the full extruding machine with two screw rods engaging of rotating Vortex entirely, and region of engagement is by 1 Increase to three, the high shear that material undergoes in runner and stretching probability greatly increase.In addition, unique center runner is horizontal Sectional area along extrusion direction in periodically ascending, then descending circulation change, to material shape into alternate stretching-shearing .
Another technical scheme of the present invention is the three-screw extruder arranged using yi word pattern, and draw ratio is more than 15.
Another technical scheme of the present invention is the multi-screw extruder using four screw extruder or more radical.
Preferably, the fusing point or flow temperature into fine phase is higher than the fusing point or flow temperature at least 25 of matrix phase ℃。
Preferably, described matrix phase is one kind in polyethylene, polypropylene, polystyrene or ABS etc., described into fibre Phase is polyamide, polyethylene terephthalate, polybutylene terephthalate (PBT), polytetrafluoroethylene (PTFE), thermotropic liquid crystal gather One kind in compound etc..
Preferably, the processing aid is antioxidant and lubricant.Primary antioxidant is 2,6- three-level butyl -4- methylphenols Or four any one in [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary anti-oxidant is powdery Phosphite ester kind antioxidant；It is fluorinated high polymer that lubricant, which includes external lubricant and in-lubricant external lubricant,；In-lubricant For low molecular weight organic compound, such as zinc stearate, barium stearate.
Preferably, matrix phase ABS drying temperatures are set as 80 DEG C in the step 1, and drying time is 4 hours；Into fibre Phase PA66 drying temperatures are set as 120 DEG C, and drying time is 8 hours；It is set as 140 DEG C into fine phase PET and PBT drying temperatures, Drying time is 10 hours；It is set as 180 DEG C into fine phase PTFE drying temperatures, drying time is 4 hours；Dried into fine phase TLCP Temperature sets 90 DEG C, 12 hours drying times.
The method that extrusion prepares in-situ micro-fibril blend a kind of directly of the present invention has advantages below：
(1) shearing-elongation flow field alternately deduced is made full use of in multi-screw extruder, synchronously realizes matrix phase and into fibre The refinement of phase is blended into the in-situ fibrillation of fine phase altogether, reduces manufacturing procedure, improves efficiency, reduces energy consumption, reduces cost, fits Answer industrialized production.
(2) temperature, screw speed, content of dispersed phase and the feeding capacity of multi-screw extruder can be jointly controlled, with quantitative Control fine micro- draw ratio in situ, realizes that fibre morphology is controllable, so as to prepare with high-strain hardening, and strain hardening coefficient is controllable In-situ micro-fibril blend.
Brief description of the drawings
For ease of being further understood to the present invention, the present invention is done in conjunction with the drawings and specific embodiments and further retouched in detail State, but do not limit the invention in any way.
The direct extrusion that Fig. 1 is the present invention prepares in-situ micro-fibril blend process chart；
The direct extrusion that Fig. 2 is the present invention prepares the del Tri-screw Extrusion used in in-situ micro-fibril blend method Machine screw rod arrangement schematic diagram (a), yi word pattern three-screw extruder screw rod arrangement schematic diagram (b), the arrangement of four screw extruder screw rod Schematic diagram (c)；
The direct extrusion that Fig. 3 is the present invention prepares the del Tri-screw Extrusion used in in-situ micro-fibril blend method Machine (TTSE) center axial tension flow field schematic diagram；
Fig. 4 is the fiber morphology SEM in situ figures in fento blend prepared by embodiment 1；
Fig. 5 is the fiber morphology SEM in situ figures in fento blend prepared by embodiment 2；
Fig. 6 is the fiber morphology SEM in situ figures in fento blend prepared by embodiment 3；
Fig. 7 is the fiber morphology SEM in situ figures in fento blend prepared by embodiment 4；
Fig. 8 is the fiber morphology SEM in situ figures in fento blend prepared by embodiment 5；
Fig. 9 is the fiber morphology SEM in situ figures in fento blend prepared by comparative example 1；
Figure 10 is the fiber morphology SEM in situ figures in fento blend prepared by comparative example 2；
Figure 11 is the fiber morphology SEM in situ figures in fento blend prepared by comparative example 3.
Figure 12 is to close section Example and tensile viscosity-time diagram (figure (a)) of comparative example and strain hardening coefficient-time System's figure (figure (b)).
Embodiment
The direct extrusion that Fig. 1 is the present invention prepares in-situ micro-fibril blend process chart.
Sample, be placed in the good solvent that temperature is matrix phase after in-situ micro-fibril blend produced by the present invention is vacuum dried Etching backflow does SEM surveys in 12~24 hours by matrix phased soln, and by undissolved in-situ micro-fibril with ethanol clean dry sample preparation Examination, fibre morphology is observed, and the fibre diameter and draw ratio in picture is counted with statistics software Image-Pro Plus 6.0, 200 fibre diameters under identical scale and corresponding length are counted, and draw ratio is calculated according to formula L/D, and is asked for averagely straight Footpath and draw ratio.
In-situ micro-fibril blend produced by the present invention mutually will all be diluted to 5% content (temperature setting ratio with banbury into fine Corresponding matrix phase fusing point is high 20 DEG C, rotating speed 50rpm, time 5min), it is 60*10* that specifications parameter (the long wide * of * are high), which is then made, 0.5mm thin slice, draft flowing deformation test (rate of extension 0.05s is carried out on Haake rheometers-1), obtain corresponding stretching Viscosity, and calculate strain hardening coefficient, wherein η by formula (1)+(t) (answered for the shear viscosity in the range of linear glutinous bullet Variable Rate is 0.001s-1Shearing initial trial obtain), corresponding data is shown in Table 1.
The HDPE- that the embodiment of the present invention produces with the polyethylene that comparative example uses for Chinese Daqing petrochemical Co., Ltd 5000S；Polypropylene is the PPH-T03 of Sinopec Yangtze petrochemical industry Co., Ltd production；Polystyrene is BASF AG's production PS 144C；ABS is the ABS HH-112 of Ben Ling high polymer materials Co., Ltd production；Polyamide 66 is BASF AG's production PA66A3HG5；Polyethylene terephthalate is the PET FR543 of DuPont production；Polybutylene terephthalate Ester is the PBT B 4500 of BASF AG's production；Polytetrafluoroethylene (PTFE) is the PTFE MP1200 of DuPont production；Polymerizable mesogenic Thing is the VA950 of Hoechst Celanese companies production；The IRGANOX1010 (four of primary antioxidant selection GIBA companies production [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester), auxiliary anti-oxidant selects what BASF AG produced IRGAFOS168 (three [2.4- di-tert-butyl-phenyls] phosphite esters)；Lubricant is produced using Ying Chuan Degussas Investment Co., Ltd Super high molecular weight organo-silicic oil Tegomer P121 or E525.
Embodiment 1
(1) dry：Matrix heterophasic polypropylene, trade mark PPH-T03,163 DEG C of fusing point (DSC, 10 DEG C/min of heating rate, temperature 24-220 DEG C of scope, N2Atmosphere)；Mutually polybutylene terephthalate (PBT)-PBT, trade mark B 4500,223 DEG C of fusing point are selected into fine (DSC, 10 DEG C/min of heating rate).PBT resin is dried 10 hours in the vacuum drying chamber that temperature is 100 DEG C.
(2) in-situ fibrillation：Raw material is blended according to mass fraction in in-situ micro-fibril dried in step (1)：PP 55%, PBT 45%, primary antioxidant 0.98%, auxiliary antioxidant 0.75%, the ratio of lubricant 3% sequentially add mixed at high speed Draw ratio is added as 28 after preliminary premixing in machine：1 del three-screw extruder, from charge door to each section of temperature of head Degree is set as：One section 150 DEG C, two sections 170 DEG C, three sections 180 DEG C, four sections 180 DEG C, five sections 180 DEG C, six sections 180 DEG C, head 180 DEG C, screw speed 100r/min, feeding capacity 7kg/h, fiber blends are 20r/ through 20 DEG C of tank quenching, and with rotating speed Min pelleter is granulated.The avarage fiber diameter and major diameter in SEM pictures are counted through statistical software Image-Pro Plus 6.0 Than being shown in Table 1.
Embodiment 2
(1) dry：Matrix phase selects polyethylene-PE, is mutually existed into fine from PA 66-PA66, PA66 resin Dried 8 hours in the vacuum drying chamber that temperature is 120 DEG C.
(2) in-situ fibrillation：Raw material is blended according to mass fraction in in-situ micro-fibril dried in step (1)：PE 80%, PA66 20%, primary antioxidant 0.72%, auxiliary antioxidant 0.63%, the ratio of lubricant 1.50% are separately added into major diameter Than for 40：1 yi word pattern three-screw extruder, it is set as from charge door to each section of temperature of head：One section 160 DEG C, two section 220 DEG C, three sections 240 DEG C, four sections 260 DEG C, five sections 260 DEG C, six sections 260 DEG C, seven sections 260 DEG C, eight sections 260 DEG C, nine sections 260 DEG C, head 260 DEG C, screw speed 200r/min, feeding capacity 6kg/h, fiber blends are through 18 DEG C of tank quenching, and with rotating speed 20r/min pelleter is granulated.Through statistical software Image-Pro Plus 6.0 count SEM pictures in fiber average diameter and Draw ratio is shown in Table 1.
Embodiment 3
(1) dry：Matrix phase selects polystyrene-PS, trade mark PS-144C, 162 DEG C of flow temperature (DMA, heating rate 3 DEG C/min, -20-200 DEG C of temperature range, N2Atmosphere) into fine polyethylene terephthalate-PET mutually is selected, PET resin exists Dried 10 hours in the vacuum drying chamber that temperature is 100 DEG C.
(2) in-situ fibrillation：Raw material is blended according to mass fraction in in-situ micro-fibril dried in step (1)：PS 70%, PET 30%, primary antioxidant 0.89%, auxiliary antioxidant 0.65%, the ratio of lubricant 2.50% sequentially add at a high speed Draw ratio is added as 28 after preliminary premixing in mixer：1 four screw extruder, set from charge door to each section of temperature of head It is set to：One section 160 DEG C, two sections 180 DEG C, three sections 190 DEG C, four sections 190 DEG C, five sections 190 DEG C, six sections 190 DEG C, 190 DEG C of head, spiral shell Bar rotating speed is 150r/min, and feeding capacity 8kg/h, fiber blends are 20r/min's through 15 DEG C of tank quenching, and with rotating speed Pelleter is granulated.The average diameter of fiber and draw ratio in SEM pictures are counted through statistical software Image-ProPlus 6.0 to be shown in Table 1。
Embodiment 4
(1) dry：Matrix phase selects ABS, mutually selects polytetrafluoroethylene (PTFE)-PTFE into fine, ABS resin is 80 DEG C in temperature Dried 4 hours in vacuum drying chamber, PTFE resin is dried 4 hours in the vacuum drying chamber that temperature is 180 DEG C.
(2) in-situ fibrillation：Raw material is blended according to mass fraction in in-situ micro-fibril dried in step (1)：ABS 75%, PTFE 25%, primary antioxidant 0.75%, auxiliary antioxidant 0.60%, the ratio of lubricant 2%, which sequentially adds, mixes at a high speed Draw ratio is added as 28 after preliminary premixing in conjunction machine：1 del three-screw extruder, from charge door to each section of head Temperature is set as：One section 150 DEG C, two sections 190 DEG C, three sections 210 DEG C, four sections 210 DEG C, five sections 210 DEG C, six sections 210 DEG C, head 210 DEG C, screw speed 120r/min, feeding capacity 7kg/h, fiber blends are through 18 DEG C of tank quenching, and with rotating speed 20r/min pelleter is granulated.Through statistical software Image-Pro Plus 6.0 count SEM pictures in fiber average diameter and Draw ratio is shown in Table 1.
Embodiment 5
(1) dry：Matrix phase selects polypropylene-PP, and mutually TLCP-TLCPVA950, TLCP are selected into fine Polymer is dried 12 hours in the vacuum drying chamber that temperature is 90 DEG C.
(2) in-situ fibrillation：Raw material is blended according to mass fraction in in-situ micro-fibril dried in step (1)：PP 95%, TLCP 5%, primary antioxidant 0.87%, auxiliary antioxidant 0.70%, the ratio of lubricant 1% are separately added into draw ratio and are 40：1 yi word pattern three-screw extruder, it is set as from charge door to each section of temperature of head：One section 150 DEG C, two sections 180 DEG C, three 220 DEG C of section, four sections 240 DEG C, five sections 240 DEG C, six sections 240 DEG C, seven sections 240 DEG C, eight sections 240 DEG C, nine sections 240 DEG C, head 240 DEG C, screw speed 180r/min, feeding capacity 6kg/h, fiber blends are 20r/ through 15 DEG C of tank quenching, and with rotating speed Min pelleter is granulated.The average diameter and major diameter of fiber in SEM pictures are counted through statistical software Image-Pro Plus 6.0 Than being shown in Table 1.
Comparative example 1
(1) dry：Matrix phase selects HOPP-PPH；Mutually polybutylene terephthalate (PBT)-PBT is selected into fine. PBT resin is dried 10 hours in the vacuum drying chamber that temperature is 100 DEG C.
(2) in-situ fibrillation：Raw material is blended according to mass fraction in in-situ micro-fibril dried in step (1)：PP 55%, PBT 45%, primary antioxidant 0.98%, auxiliary antioxidant 0.75%, the ratio of lubricant 3% sequentially add mixed at high speed Draw ratio is added as 40 after preliminary premixing in machine：1 W＆P meshing co rotating twin screw extrusions, it is each from charge door to head Duan Wendu is set as：One section 150 DEG C, two sections 170 DEG C, three sections 180 DEG C, four sections 180 DEG C, five sections 180 DEG C, six sections 180 DEG C, seven sections 180 DEG C, eight sections 180 DEG C, nine sections 180 DEG C, 180 DEG C, screw speed 250r/min, feeding capacity 6kg/h of head, fiber blend Thing is through 20 DEG C of tank quenching, and the pelleter for being 20r/min with rotating speed is granulated.Through statistical software Image-Pro Plus 6.0 The average diameter of fiber and draw ratio are shown in Table 1 in statistics SEM pictures.
Comparative example 2
(1) dry：Matrix phase selects high density polyethylene (HDPE)-PE, and mutually PA 66-PA66, PA66 are selected into fine Resin is dried 8 hours in the vacuum drying chamber that temperature is 120 DEG C.
(2) in-situ fibrillation：Raw material is blended according to mass fraction in in-situ micro-fibril dried in step (1)：PE 80%, PA66 20%, primary antioxidant 0.72%, auxiliary antioxidant 0.63%, the ratio of lubricant 1.50% sequentially add at a high speed Draw ratio is added as 40 after preliminary premixing in mixer：1 W＆P meshing co rotating twin screw extrusions, from charge door to machine Each section of temperature is set as：One section 150 DEG C, two sections 190 DEG C, three sections 240 DEG C, four sections 260 DEG C, five sections 260 DEG C, six sections 260 DEG C, Seven sections 260 DEG C, eight sections 260 DEG C, nine sections 260 DEG C, 260 DEG C, screw speed 300r/min, feeding capacity 6kg/h of head, fiber Blend is through 20 DEG C of tank quenching, and the pelleter for being 20r/min with rotating speed is granulated.Through statistical software Image-Pro Plus Average fibre diameter and draw ratio are shown in Table 1 in 6.0 statistics SEM pictures.
Comparative example 3
(1) dry：Matrix phase selects polystyrene-PS, and mutually polyethylene terephthalate-PET, PET are selected into fine Resin is dried 10 hours in the vacuum drying chamber that temperature is 100 DEG C.
(2) in-situ fibrillation：Raw material is blended according to mass fraction in in-situ micro-fibril dried in step (1)：PS 70%, PET 30%, primary antioxidant 0.89%, auxiliary antioxidant 0.65%, the ratio of lubricant 2.50% sequentially add at a high speed Draw ratio is added as 26 after preliminary premixing in mixer：1 Leistriz double screw extruders, it is each from charge door to head Duan Wendu is set as：One section 160 DEG C, two sections 210 DEG C, three sections 235 DEG C, four sections 235 DEG C, five sections 235 DEG C, six sections 235 DEG C, head 235 DEG C, screw speed 160r/min, feeding capacity 5kg/h, fiber blends are through 20 DEG C of tank quenching, and with rotating speed 20r/min pelleter is granulated.Through statistical software Image-Pro Plus 6.0 count SEM pictures in fiber average diameter and Draw ratio is shown in Table 1.
Average fibre diameter and draw ratio in the fento blend of table 1
There is less diameter and bigger draw ratio, flexible fento phase using the TTSE in-situ micro-fibril composites prepared It is dispersed in matrix phase, and netted entanglement occurs and forms spacial framework, the melt for greatly improving matrix phase glues Property and intensity, have it is excellent apply hardening characteristics, this is highly beneficial to blown film, biaxial tension and foaming forming technique.

Claims (8)

  1. A kind of 1. method that directly extrusion prepares in-situ micro-fibril blend, it is characterised in that comprise the following steps：
    Step 1：By by the relatively low thermoplastic matrix resin of fusing point or flow temperature, fusing point or the higher thermoplasticity of flow temperature into The in-situ micro-fibril blending raw material of fiberized resin and processing aid composition, which is placed in vacuum drying chamber, to be separately dried；
    Step 2：Raw material is blended according to mass fraction, matrix phase content 95-55%, into fibre in the dried in-situ micro-fibril Phase content 5-45%, processing aid 0-5% ratio be separately added into screw rod radical more than 2 multi-screw extruder in, or by than Add in multi-screw extruder of the screw rod radical more than 2 after preliminary premixing in example addition high-speed mixer, squeezed in multiscrew Go out melt temperature in machine to be less than into melting extrusion under the fusing point of fine gathering compound or flow temperature process conditions, immerse tank afterwards Middle cooling treatment, is granulated through pelleter, prepares in-situ micro-fibril blend.
  2. 2. according to the method for claim 1, it is characterised in that the multi-screw extruder be draw ratio more than 15 fall three Angular full engagement three-screw extruder.
  3. 3. according to the method for claim 1, it is characterised in that the multi-screw extruder is the word that draw ratio is more than 15 Type engages three-screw extruder entirely.
  4. 4. according to the method for claim 1, it is characterised in that the multi-screw extruder is four screw extruder.
  5. 5. according to the method for claim 1, it is characterised in that the fusing point or flow temperature into fine phase is higher than the base At least 25 DEG C of the fusing point or flow temperature of body phase.
  6. 6. according to the method for claim 1, it is characterised in that described matrix mutually for polyethylene, polypropylene, polystyrene or One kind in ABS, it is described into it is fine be mutually polyamide, polyethylene terephthalate, polybutylene terephthalate (PBT), poly- four One kind in PVF, liquid crystal polymer.
  7. 7. according to the method for claim 1, it is characterised in that melt temperature in the multi-screw extruder than it is described into Fine gathering compound fusing point or flow temperature are low 5 DEG C -60 DEG C, higher than 20 DEG C of described matrix gathering compound fusing point or flow temperature with On.
  8. 8. according to the method for claim 1, it is characterised in that in described the step of immersing cooling treatment in tank, leaching Enter quenching in the tank that temperature is 5~25 DEG C to handle.
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CN111320809A (en) * 2018-12-14 2020-06-23 朴哲范 In-situ fiber-forming nano fiber reinforced polymer composite particle material
CN111875881B (en) * 2020-07-16 2023-05-09 广东工业大学 Method for selectively distributing lamellar nano-sheets at interface of incompatible blend and nano-composite material
CN115304853B (en) * 2022-07-13 2023-04-21 贵州省材料产业技术研究院 Microfiber reinforced polymer composite material with in-situ abnormal structure and preparation method thereof
CN115558205A (en) * 2022-10-19 2023-01-03 株洲时代工程塑料科技有限责任公司 Polypropylene composite material with low linear expansion coefficient and preparation method thereof

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CA1216119A (en) * 1984-05-16 1987-01-06 Mitsui Chemicals, Incorporated Process for producing stretched article of ultrahigh- molecular weight polyethylene
US5225488A (en) * 1991-05-01 1993-07-06 Virginia Polytechnic Institute & State University Mixing process for generating in-situ reinforced thermoplastics
CN101423615A (en) * 2007-10-29 2009-05-06 文彦飞 A kind of method that improves thermoplastic polymer fused mass strength

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